Amphiphilic compounds with a plurality of hydrophilic and hydrophobic groups based on carbonic acid derivatives

ABSTRACT

The invention relates to amphiphilic compounds of the general formula I ##STR1## which have at least two hydrophilic and at least two hydrophobic groups and are based on carbonic acid derivatives. 
     The spacer A is an aliphatic, cyclic or acyclic or an aromatic di-, oligo- or polycarbonate of the formula II: ##STR2## The amphiphilic compounds according to this invention are mostly surface-active and are suitable as emulsifiers, demulsifiers, detergents, dispersants and hydrotropes for industrial and domestic use, in particular in the fields of metalworking, ore extraction, surface finishing, plastics processing, washing and cleaning, cleaning of hard surfaces, manual dishwashing compositions, cosmetics, medicine and food processing and preparation.

This application is a 371 of PCT/EP96/04979 filed Nov. 14, 1996.

The invention relates to amphiphilic compounds containing a plurality ofhydrophilic and hydrophobic groups, based on carbonic acid derivatives.

Known amphiphilic substances encompass a wide variety of anionic,cationic, nonionic and zwitterionic compounds. By far the majority ofthese substances consist of a hydrophilic head group and at least onehydrophobic part.

With amphiphilic substances there is a need, for ecological reasons, forexample reduction packaging and transportation, to achieve anincreasingly greater effect per unit mass of substance employed. Sinceoptimization by mixing amphiphilic substances produces only very limitedadvances, novel amphiphilic substances with greater effectiveness arerequired. It is therefore necessary in particular to find substanceswith lower critical micelle concentrations and/or lower surface tensionsin order to be able to reduce markedly the amounts of active substanceemployed. Initial approaches to a solution in the direction ofhigher-performance amphiphilic substances by doubling one part of thestructure (hydrophilic head group, hydrophobic group) are already known.Thus, cationic surface-active compounds can be obtained by addinglong-chain alkyl halides onto permethylated alkylenediamines [R. Zana,M. Benrraou, R. Rueff, Langmuir, 7 (1991)1072; R. Zana, Y. Talmon,Nature, 362 (1993) 228; E. Alami, G. Beinert, P. Marie, R. Zana,Langmuir, 9 (1993) 1465].

Anionic surface-active compounds containing at least two hydrophilicgroups and at least two hydrophobic groups have to date been preparedonly on the basis of diglycidyl ethers (U.S. Pat. No. 5,160,450, JP 01304 033, JP 4 124 165). However, diglycidyl ethers are regarded astoxicologically objectionable and are rather costly. Furthermore,epichlorohydrin is used for their preparation, which leads to largeamounts of residues so that these compounds are no longer up to datefrom ecotoxicological and economic viewpoints.

The object was therefore to find amphiphilic compounds which have atleast two hydrophilic groups and at least two hydrophobic groups, arevery effective relative to the amount used, and furthermore can beprepared from raw materials which are readily available industrially andwithout large amounts of unwanted by-products being formed. In addition,the compounds should be easy to cleave again.

The object is achieved according to the invention by amphiphilic di-,oligo- or polycarbonates whose basic skeleton can be prepared from di-,oligo- or polycarbonic acid derivatives and alkoxylated fatty amines andfatty acid amides. The corresponding di-, oligo- or polycarbonates arenonionic surfactants which, nevertheless, can be further reacted to giveanionic amphiphilic compounds. In this context, suitable reactions aresulfonation, carboxymethylation and conversion to, for example,isethionates, taurates and sulfosuccinates.

The amphiphilic compounds according to the invention are thus compoundsof the general formula I: ##STR3## in which R¹ and R², independently ofone another, are an unbranched or branched, saturated or unsaturatedhydrocarbon radical having from 1 to 22, preferably from 6 to 18, carbonatoms and an unbranched or branched, saturated or unsaturated acylradical having from 2 to 23, preferably from 7 to 19, carbon atoms, nand m, independently of one another, are at least 1 and the sum of n andm is a number from 2 to 200, preferably from 2 to 100 and particularlypreferably from 2 to 10.

a, b, c, d, e, f, g and h are, independently of one another, numbersfrom 0 to 15, and the sum of a and b, c and d, e and f and g and h mustin each case be at least 1. The alkoxide units are incorporated randomlyor blockwise, and the sequence is arbitrary. Y and Z. independently ofone another, are hydrogen or functional groups. Functional groups whichmay be mentioned are --CH₂ COOM, --SO₃ M, --C₂ H₄ SO₃ M, --C(O)C₂ H₃(SO₃ M)COOM', --P(O)(OM)₂, where M and M' are alkali metal, ammonium,alkanolammonium or 1/2 alkaline earth metal.

Specific radicals which may be mentioned as substituents R¹ and R² aremethyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl,n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl,n-eicosyl, n-uneicosyl, n-docosyl and their branched-chain isomers, andthe corresponding mono-, di- or triunsaturated radicals and thecorresponding acyl compounds.

The spacer A is an aliphatic, cyclic or acyclic or an aromatic di-,oligo- or polycarbonate of the formula II: ##STR4##

R originates from a di-, oligo- or polyol which, preferably, does nottend toward cyclization, in which r hydroxyl groups are esterified withcarbonic acid derivatives. r is a number from 2 to 200, preferably from2 to 20, particularly preferably from 2 to 10. Examples thereof whichmay be mentioned here are alkylenediols, preferably having from 2 to 8carbon atoms, di- to tetraethylene glycols, di- to tetrapropyleneglycols, polyalkylene glycols, such as, for example polyethyleneglycols, oligo- or polyglycerols, sorbitol, polyvinyl alcohol,trimethylolpropane and acetals such as2,2'-methylene-bis(1,3-dioxolane-5-methylene)diol. For stoichiometricreasons, r=n+m.

The amphiphilic compounds according to the invention are distinguishedby extremely low critical micelle concentrations (CMCs) and very lowsurface tensions, which must be attributed to their specialstructure--at least two hydrophilic groups and at least two hydrophobicgroups. Furthermore, most of them have a rather high hydrophilicsuspension capacity which is about halfway between that of conventionalsurfactants and that of pentasodium tripolyphosphate. Some of thesecompounds are extremely rapid wetting agents. They all have very highhardness stability and good solubility in water.

The amphiphilic compounds according to this invention are particularlysuitable as emulsifiers, demulsifiers, detergents, dispersants,hydrotropes and antistatics in industry and domestically, for example inthe areas of metalworking, ore extraction, textile auxiliaries, surfacefinishing, plastics processing, washing and cleaning, cleaning of hardsurfaces, in particular as a manual dishwashing detergent, cosmetics,medicine and foods processing and preparation.

In these cases they can be combined with all customary anionic,nonionic, cationic and ampholytic surface-active substances.

Examples which may be mentioned of nonionic surface-active substanceswhich can be used for a combination are: fatty acid glycerides, fattyacid polyglycerides, fatty acid esters, ethoxylates of higher alcohols,polyoxyethylene fatty acid glycerides, polyoxy-ethylene/propylene glycolfatty acid esters, polyoxy-ethylene sorbitan fatty acid esters,polyoxyethylene castor oil or hydrogenated castor oil derivatives,polyoxyethylene lanolin derivatives, polyoxyethylene fatty acid amides,polyoxyethylene alkylamines, alkanolamines, alkylamine oxides,derivatives of protein hydrolysates, hydroxy-mixed ethers,alkylpolyglycosides, amine oxides and alkylglucamides.

Examples which may be mentioned of anionic surface-active substanceswhich can be used for combinations are: soaps, ether carboxylic acidsand salts thereof, alkyl-sulfonates, α-olefinsulfonates, α-sulfofattyacid derivatives, sulfonates of higher fatty acid esters, higher alcoholsulfates, alcohol ether sulfates, hydroxy-mixed ether sulfates, salts ofphosphate esters, taurides, isethionates, linearalkyl-benzenesulfonates, cumenesulfonate, alkylarylsulfonates, sulfatesof polyoxyethylene fatty acid amides and salts of acylamino acids.

Examples which may be mentioned of customary cationic surface-activesubstances which can be used for combinations are:alkyltrimethylammonium salts, dialkyl-dimethylammonium salts,alkyldimethylbenzylammonium salts, alkylpyridinium salts,alkylisoquinolinium salts, benzethonium chlorides and cationic acylaminoacid derivatives.

Examples which may be mentioned of ampholytic surface-active substanceswhich can be used for combinations are: amino acids, betaines,sulfobetaines, imidazoline derivatives, soybean oil lipids and lecithin.

Furthermore, the amphiphilic compounds according to the invention can bealso be combined together on their own.

It is likewise possible to add conventional additives to the amphiphiliccompounds according to the invention. Such additives are specificallyselected for a formulation and for example comprise inorganic salts,such as sodium chloride and sulfate, and builders, hydrotropes, UVabsorbers, softening agents, chelating agents, viscosity modifiers andfragrances.

The abovementioned compounds can be prepared from di-, oligo- orpolycarbonates and at least two equivalents of alkoxylated fatty aminesand/or alkoxylated fatty acid amides. The precursors used here are thedi-, oligo- or polyols which can be reacted with one equivalent ofdiethyl carbonate per hydroxyl group. There must be at least twoequivalents of diethyl carbonate, in the case of oligo- or polyols theproperties of the molecule can be adjusted more exactly by the degree ofconversion with carbonate or amine ethoxylate or amide ethoxylate in thelast step. Both of the esterification and transesterification reactionsdescribed above, can be carried out using known catalysts, such as, forexample, titanates, mixtures of antimony trioxide and calcium acetate,stannates, zinc acetate and alkali metal oxides. Titanates have,however, proven to be particularly favorable as regards reaction timesand colour quality. The anionic amphiphilic compounds can be prepared byreacting the aforementioned products with, for example, amidosulfonicacid, chloroacetic acid salts, isethionates or maleic anhydride, andneutralizing the resulting mixture with aqueous alkali metal or alkalineearth metal hydroxides, aqueous ammonia or alkanolamines. If required,the products are bleached in aqueous solution with hydrogen peroxide(0.1 to 2.0%, based on solid).

What is claimed is:
 1. An amphiphilic compound of the general formula I##STR5## in which R¹ and R², independently of one another, are anunbranched or branched, saturated or unsaturated hydrocarbon radicalhaving from 1 to 22 carbon atoms or an unbranched or branched, saturatedor unsaturated acyl radical having from 2 to 23 carbon atoms, A is adi-, oligo- or polycarbonate, and Y and Z are hydrogen or a functionalradical --CH₂ COOM, --SO₃ M, --C₂ H₄ SO₃ M, --C₂ H₄ SO₃ M, --C(O)C₂ H₃(SO₃ M)COOM' or --P(O)(OM)₂ where M, M'=alkali metal, ammonium,alkanolammonium or 1/2 alkaline earth metal, and in which n and m,independently of one another, are each at least 1, the sum of n and m isfrom 2 to 200 and a, b, c, d, e, f, g and h, independently of oneanother, are from 0 to 15, and the sum of a and b, c and d, e and f andg and h must in each case be at least
 1. 2. The amphiphilic compound asclaimed in claim 1, wherein the spacer A satisfies the general formula(II):

    R(OC(O)).sub.r

wherein R is derived from a di-, oligo- or polyol, and r is a numberfrom 2 to
 200. 3. The amphiphilic compound as claimed in claim 2,wherein R is derived from a di-, tri- or polyethylene glycol.
 4. Theamphiphilic compound as claimed in claim 1, whereinthe hydrocarbonradicals R¹ and R² in the formula I, independently of one anothercontain from 6 to 18 carbon atoms, and the acyl radicals, independentlyof one another, contain from 7 to 19 carbon atoms.
 5. The amphiphiliccompound as claimed in one of claim 1, whereinY and Z, independently ofone another, are hydrogen or a functional radical --CH₂ COOM, --SO₃ M,--C₂ H₄ SO₃ M, --C(O)C₂ H₃ (SO₃ M)COOM' or --P(O)(OM)₂ where M,M'=alkali metal, ammonium, alkanolammonium or 1/2 alkaline earth metal.6. A composition comprising at least one amphiphilic compound of thegeneral formula I as claimed in claim
 1. 7. The composition of claim 6,comprising two or more of said amphiphilic compound.
 8. A compositioncomprising at least one amphiphilic compound of the general formula asclaimed in claim 1, and a surface active substance selected from thegroup consisting of anionic, nonionic, cationic and ampholytic surfaceactive substances.
 9. A composition comprising a mixture of homologuesof at least two amphiphilic compounds of the general formula as claimedin claim
 1. 10. In a process of emulsifying, the improvement comprisingemulsifying with the amphiphilic compound of claim 1 as the emulsifier.11. In a process of demulsifing, the improvement comprising demulsifyingwith the amphiphilic compound of claim 1 as the demulsifier.
 12. In aprocess of metalworking, the improvement comprising metalworking withthe amphiphilic compound of claim 1 as a processing auxiliary.
 13. In aprocess of ore extraction, the improvement comprising ore extractingwith the amphiphilic compound of claim 1 as a processing auxiliary. 14.In a process of surface finishing, the improvement comprising surfacefinishing with the amphiphilic compound of claim 1 as a processingauxiliary.
 15. In a process of manufacturing plastics, the improvementcomprising manufacturing plastics with the amphiphilic compound of claim1 as a processing auxiliary.
 16. In a process of processing plastics,the improvement comprising processing plastics with the amphiphiliccompound of claim 1 as a processing auxiliary.
 17. In a process ofcleaning or washing textiles, the improvement comprising cleaning orwashing textiles with the amphiphilic compound of claim 1 as a textileauxiliary.
 18. In a process of cleaning hard surfaces, the improvementcomprising cleaning hard surfaces with the amphiphilic compound of claim1 as a cleaning material.
 19. In a process of manual dishwashing, theimprovement comprising manually dishwashing with the amphiphiliccompound of claim 1 as a cleaning material.
 20. In a process of cleaningor washing skin or hair, the improvement comprising cleaning or washingskin or hair with the amphiphilic compound of claim 1 as a cleaningmaterial.